WO2007080763A1 - Pile a combustible a polymere solide - Google Patents

Pile a combustible a polymere solide Download PDF

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Publication number
WO2007080763A1
WO2007080763A1 PCT/JP2006/325540 JP2006325540W WO2007080763A1 WO 2007080763 A1 WO2007080763 A1 WO 2007080763A1 JP 2006325540 W JP2006325540 W JP 2006325540W WO 2007080763 A1 WO2007080763 A1 WO 2007080763A1
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WIPO (PCT)
Prior art keywords
electrode
fuel cell
fuel
membrane
polymer electrolyte
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PCT/JP2006/325540
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English (en)
Japanese (ja)
Inventor
Kenji Kobayashi
Tetsuaki Hirayama
Hideaki Sasaki
Original Assignee
Nec Corporation
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Filing date
Publication date
Application filed by Nec Corporation filed Critical Nec Corporation
Priority to US12/160,985 priority Critical patent/US7923164B2/en
Priority to CN2006800512200A priority patent/CN101361216B/zh
Priority to JP2007553863A priority patent/JP5182559B2/ja
Publication of WO2007080763A1 publication Critical patent/WO2007080763A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a polymer electrolyte fuel cell.
  • the polymer electrolyte fuel cell is small and lightweight, it is actively researched and developed as a power source for various electronic devices such as portable devices.
  • a polymer electrolyte fuel cell includes an electrode electrolyte membrane assembly (MEA) having a structure in which a solid polymer electrolyte membrane is sandwiched between an anode and a force sword.
  • MEA electrode electrolyte membrane assembly
  • a fuel cell of a type that supplies fuel directly to the anode is called a direct fuel cell, and decomposes the supplied fuel on a catalyst supported on the anode to generate cations, electrons, and intermediate products. .
  • the generated cations permeate the solid polymer electrolyte membrane and move to the force sword side, and the generated electrons move to the force sword side through an external load, and these are moved by air to the force sword. It reacts with the oxygen in it to generate electricity.
  • DMFC direct methanol fuel cell
  • DMFC direct methanol fuel cell
  • the force sword reaction represented by That is, in DMFC, in theory, 1 mol of methanol and 1 mol of water react with each other to produce 1 mol of reaction product (carbon dioxide). At this time, since hydrogen ions and electrons are also generated, the theoretical concentration of methanol in the methanol aqueous solution, which is the fuel, is about 70 vol% in volume%.
  • the fuel permeation layer 106 for introducing fuel into the cell by capillary force is disposed between the anode 102 and the fuel permeation layer 106 and introduced into the cell.
  • the fuel introduced into the liquid fuel introduction path 110 is supplied from the side surface of the stack 109 to the fuel permeation layer 106 by capillary force, further vaporized by the fuel vaporization layer 107, and supplied to the anode 102.
  • the separator 105, the fuel permeation layer 106, and the fuel vaporization layer 107 also function as a current collecting plate that conducts the generated electrons.
  • the fuel permeation layer 106 is formed of a carbon conductive material.
  • a methanol and water 1: 1 mixture (molar ratio) is used as the fuel, and the fuel is supplied from the fuel storage tank to the liquid fuel introduction path 110 by using the tank of the power generation unit. It may be configured such that the fuel is pushed out by the natural fall by being provided at the top, the internal pressure in the tank, or the like, or the fuel can be drawn out by the capillary force of the liquid fuel introduction passage 110. It is said.
  • JP-A-2001-15130 the use of a porous body whose surface is made of a fluororesin and whose surface is made of a material having a thermal conductivity of 20 W / m'K or more is used for the separation membrane. It has been shown that liquid fuel is vaporized and supplied by heat of vaporization.
  • Patent Document 1 In the configuration in Japanese Patent Application Laid-Open No. 2000-106201, a 1: 1 mixture (molar ratio) of methanol and water is used, and liquid fuel can be supplied to the fuel vaporization layer 107 by internal pressure in the tank or the like.
  • the present inventors have found that the configuration of Patent Document 1 cannot provide a stable fuel supply. That is, in such fuel supply by capillary force, a methanol aqueous solution having a higher concentration than the liquid fuel is supplied when a high-concentration methanol aqueous solution is used from the equilibrium state between the liquid phase and the gas phase. In other words, stable power generation using a high-concentration aqueous methanol solution becomes difficult. Further, with this fuel supply method, complete vaporization supply is difficult, and the portion supplied as a liquid causes crossover. For these reasons, it has been difficult to use high-concentration methanol aqueous solution as fuel.
  • Japanese Patent Application Laid-Open No. 2004-79506 describes a technique for providing a liquid fuel cell that is small and can stably generate power.
  • Japanese Patent Application Laid-Open No. 2002-289224 describes a technique that aims to provide a fuel cell that can solve the problem of reduced power generation efficiency caused by gas generation near the output terminal and can provide higher output.
  • Japanese Patent Laid-Open No. 2000-268836 can prevent crossover of liquid fuel, and can stably supply fuel to the negative electrode even if the liquid fuel decreases or the vertical positional relationship fluctuates. Technologies for providing power generation devices that can be used are described.
  • An object of the present invention is to provide a polymer electrolyte fuel cell that suppresses crossover.
  • Another object of the present invention is to provide a polymer electrolyte fuel cell having high power generation characteristics when a high concentration fuel is used.
  • Still another object of the present invention is to provide a polymer electrolyte fuel cell that suppresses fuel consumption.
  • a solid polymer fuel cell includes an electrode / electrolyte membrane assembly that generates electric power by a chemical reaction between an aqueous fuel solution and an oxidant, a hydrophilic membrane formed from a hydrophilic material, and a water repellent property. And a water-repellent porous film formed by the material strength of The water repellent porous membrane is disposed between the electrode / electrolyte membrane assembly and the hydrophilic membrane.
  • the aqueous fuel solution is supplied to the electrode / electrolyte membrane assembly through the hydrophilic membrane and the water-repellent porous membrane. Its burning Examples of the material include methanol.
  • the hydrophilic film vaporizes the aqueous fuel solution while exuding the aqueous fuel solution slightly as a liquid.
  • the water-repellent porous membrane supplies vaporized fuel and water to the electrode-electrolyte membrane assembly without allowing the aqueous fuel solution to directly contact the electrode-electrolyte membrane assembly for its water repellency.
  • the polymer electrolyte fuel cell according to the present invention can prevent excessive permeation of fuel even when a high concentration aqueous fuel solution is used, and supplies an optimal amount of fuel and water to the electrode-electrolyte membrane assembly. be able to.
  • the solid polymer fuel cell according to the present invention can prevent water shortage at the anode and increase in the crossover of fuel to the power sword, can suppress deterioration in characteristics, and can provide sufficient power generation characteristics. The ability to obtain S.
  • the polymer electrolyte fuel cell can prevent the hydrophilic membrane and the water-repellent porous membrane from coming into close contact with each other and prevent the fuel and water from being vaporized and supplied.
  • the polymer electrolyte fuel cell further includes a perforated plate in which a plurality of holes are formed. The perforated plate is disposed between the hydrophilic film and the water repellent porous film.
  • the electrode-electrolyte membrane assembly includes a force sword to which an oxidant is supplied, an anode to which an aqueous fuel solution is supplied, and a solid polymer electrolyte membrane disposed between the force sword and the anode.
  • the sealing material for isolating the anode from the outside has a vent hole through which carbon dioxide generated by a chemical reaction passes.
  • the polymer electrolyte fuel cell is preferable because it prevents an increase in the internal pressure of the anode and prevents the supply of fuel and water to the anode by the carbon dioxide.
  • the sealing material further electrically insulates the current collector that transmits electrons from the anode and the solid polymer electrolyte membrane.
  • the vent is preferably formed in such a single material.
  • the electrode-electrolyte membrane assembly includes a force sword to which an oxidant is supplied, an anode to which an aqueous fuel solution is supplied, and a solid polymer electrolyte membrane disposed between the force sword and the anode. ing.
  • the polymer electrolyte fuel cell according to the present invention further includes an evaporation suppression layer that suppresses evaporation of water.
  • the evaporation suppression layer is disposed between the force sword and the outside.
  • the polymer electrolyte fuel cell can prevent the water generated by the force sword from evaporating into the atmosphere, and the non-evaporated water is back-diffused to the anode, thereby reducing the water consumption on the fuel side. Can be reduced.
  • the polymer electrolyte fuel cell can utilize a high-concentration aqueous methanol solution.
  • the evaporation suppression layer is preferably formed from a hydrophilic material, or is preferably formed from a hydrophobic material.
  • the polymer electrolyte fuel cell according to the present invention can suppress crossover, improve power generation characteristics, and suppress fuel consumption when a high concentration fuel is used.
  • FIG. 1 is a cross-sectional view showing an embodiment of a polymer electrolyte fuel cell according to the present invention.
  • FIG. 2 is an exploded perspective view showing an embodiment of a polymer electrolyte fuel cell according to the present invention.
  • FIG. 3 is a graph showing current-voltage characteristics of a polymer electrolyte fuel cell.
  • FIG. 4 is a cross-sectional view showing a known polymer electrolyte fuel cell.
  • the polymer electrolyte fuel cell 10 has a cell structure, and as shown in FIG. 1, the cell structure is composed of an anode side collector electrode 1, a force sword side collector electrode 2, and an electrode electrolyte membrane assembly. (MEA, Menbrane and Electrode Assembly) 3.
  • the anode side collecting electrode 1 is made of stainless steel and has a plate shape.
  • the force sword side collecting electrode 2 is made of stainless steel and is formed in a plate shape.
  • the electrode-electrolyte membrane assembly 3 is formed in a plate shape.
  • the electrode-electrolyte membrane assembly 3 includes a solid polymer electrolyte membrane 5, an anode electrode 6, and a force sword electrode 7.
  • the solid polymer electrolyte membrane 5 is disposed between the anode electrode 6 and the force sword electrode 7.
  • the solid polymer electrolyte membrane 5 is formed from an organic polymer exhibiting proton conductivity.
  • An example of the organic polymer is “Nafion 117” (registered trademark) manufactured by DuPont.
  • the anode electrode 6 is formed of a catalyst layer and a porous substrate, and is formed in a plate shape.
  • the catalyst layer is formed of a catalyst, a support and a polymer electrolyte.
  • the catalyst is fine particles formed from a noble metal and is supported on the support. Examples of the noble metal include simple metals and alloys. Examples of the catalyst include a alloy containing platinum and ruthenium (for example, an alloy having a ruthenium ratio of 60 at%).
  • the diameter of the fine particles is preferably 3 nm to 5 nm.
  • the carrier is exemplified by carbon particles formed from carbon. Examples of the carbon particles include “Ketjen Black, EC600JDJ (registered trademark)” manufactured by Lion.
  • the polymer electrolyte has proton conductivity.
  • “DuPont” An example is Nafion, DE521J (registered trademark), which is a material having a low electrical resistance and a large number of holes formed therein.
  • a paper is exemplified, and “TGP-H-120” manufactured by Torayen Earth is exemplified.
  • the anode electrode 6 is disposed on the anode-side collector electrode 1 side of the electrode-electrolyte membrane assembly 3 and is electrically connected to the anode-side collector electrode 1.
  • the force sword electrode 7 is formed of a catalyst layer and a porous substrate, and is formed in a plate shape.
  • the catalyst layer is formed of a catalyst, a support and a polymer electrolyte.
  • the catalyst is fine particles formed from a noble metal and is supported on the support. Examples of the noble metal include simple metals and alloys. An example of the catalyst is platinum.
  • the diameter of the fine particles is preferably 3nm to 5nm.
  • Examples of the carrier include carbon particles formed from carbon. Examples of the carbon particles include “Ketjen Black, EC600JDJ (registered trademark)” manufactured by Lion.
  • the polymer electrolyte has proton conductivity.
  • the polymer electrolyte is manufactured by DuPont.
  • the porous base material is a material having a low electrical resistance and a large number of holes.
  • carbon is used.
  • Paper is exemplified, and “TGP_H_120” manufactured by Toray Industries, Inc. is exemplified.
  • the force sword electrode 7 is disposed on the force sword side collector electrode 2 side of the electrode-electrolyte membrane assembly 3 and is electrically connected to the force sword side collector electrode 2.
  • the electrode-electrolyte membrane assembly 3 further includes insulating and sealing materials 11 and 12.
  • the insulating and sealing material 11 is made of an insulator. As the insulator, silicon rubber is exemplified.
  • the insulating and sealing material 11 is disposed between the anode-side collector electrode 1 and the solid polymer electrolyte membrane 5 so that the anode-side collector electrode 1 and the solid polymer electrolyte membrane 5 are electrically insulated. ing.
  • the insulating and sealing material 11 further seals the anode electrode 6 from the outside so that the anode electrode 6 is not exposed to the outside air.
  • the insulating and sealing material 11 further has a carbon dioxide gas discharge port 14 formed therein.
  • the carbon dioxide gas discharge port 14 releases carbon dioxide generated by the anode electrode 6 to the outside.
  • the insulating and sealing material 12 is made of an insulator. As the insulator, silicon rubber is exemplified.
  • the insulating and sealing material 12 is provided between the force sword side collector electrode 2 and the solid polymer electrolyte membrane 5 so that the force sword side collector electrode 2 and the solid polymer electrolyte membrane 5 are electrically insulated. Is arranged. The insulating and sealing material 12 further seals the force sword electrode 7 from the outside so that the force sword electrode 7 is not exposed to the outside air.
  • the polymer electrolyte fuel cell 10 further includes a fuel tank 15, a fuel holding unit 16, a separation membrane 20, and a moisturizing material 21.
  • the fuel tank 15 is a container formed of polypropylene, and is disposed on the anode-side collector electrode 1 side of the cell structure of the polymer electrolyte fuel cell 10.
  • the fuel tank 15 stores fuel therein.
  • the fuel is a liquid containing water and methanol.
  • An example of the liquid is a 50 vol% methanol aqueous solution.
  • the fuel holding portion 16 is formed of a wiking material that sucks up the liquid by wiking and is disposed inside the fuel tank 15. Examples of the kingking material are urethane materials.
  • the separation membrane 20 is formed in a sheet shape, and is disposed between the anode side collecting electrode 1 and the fuel tank 5.
  • the separation membrane 20 includes a hydrophilic membrane 17, a water repellent porous membrane 18, and a perforated plate 19.
  • the hydrophilic film 17 is made of a hydrophilic material and is formed in a sheet shape. Examples of the hydrophilic film 17 include an ion exchange membrane formed from a molecule having a sulfone group, and examples thereof include “naphth ions” and styrene dibutene benzene-based membranes.
  • the styrene dibule benzene film is a material obtained by sulfonating a styrene dibule benzene copolymer.
  • the water content of the hydrophilic film 17 is preferably about 10% to 40%.
  • the thickness of the hydrophilic membrane 17 is Depending on the concentration of the fee, for example, 20! About 300 zm is desirable.
  • the material of the hydrophilic film 17 can be formed of a material different from that of the ion exchange membrane. As long as the material is supplied with methanol and water from the fuel tank 15 to the electrode-electrolyte membrane assembly 3, the permeation rate is greater than the amount that the electrode-electrolyte membrane assembly 3 consumes methanol and water. Any material can be applied.
  • the hydrophilic film 17 is in contact with the fuel holding part 16.
  • the water-repellent porous film 18 is formed of a water-repellent material and is formed in a sheet shape.
  • the water repellent porous film 18 is formed of a porous body.
  • the porous body include those formed from a fluororesin and those processed into a porous body.
  • An example of the fluororesin is PTFE.
  • the material of the porous body to be surface-treated include metals, plastics, and ceramics.
  • the surface treatment is exemplified by applying a water repellent material.
  • the water-repellent material applied include PTFE, perfluoroalkoxyalkane (PFA), and ethylene-tetrafluoroethylene copolymer (ETFE) force S.
  • the thickness of the water-repellent porous film 18 is determined according to the speed at which the fuel is supplied to the anode electrode 6 and the heat conduction of the heat of vaporization that vaporizes the fuel, and is desirably 100 / m or less, for example.
  • the porosity of the water repellent porous film 18 is preferably about 60% to 90%.
  • the air permeability of the water repellent porous film 18 is preferably 20 seconds or less. Note that the material of the water repellent porous film 18 can be formed of a material different from such a material.
  • the water repellent porous membrane 18 is in contact with the fuel holding portion 16 through a hole formed in the anode-side collector electrode 1.
  • the perforated plate 19 is a sheet formed of stainless steel, and has a plurality of holes.
  • the perforated plate 19 is disposed between the hydrophilic film 17 and the water repellent porous film 18.
  • the perforated plate 19 desirably has a thickness force of about SO.lmm to 2 mm, and desirably has an aperture ratio of 50 to 90%.
  • the perforated plate 19 provides a space of 0.1 mm or more between the hydrophilic film 17 and the water-repellent porous film 18 to prevent the hydrophilic film 17 and the water-repellent porous film 18 from sticking to each other. ing .
  • the perforated plate 19 provides such a physical space between the hydrophilic membrane 17 and the water-repellent porous material 18.
  • the perforated plate 19 is easily affected by a low temperature or the like at which the diffusion capacity is greatly reduced when the plate thickness or the aperture ratio is not appropriate. Further, the perforated plate 19 also functions as a porous body holding body, which leads to suppression of fluctuations in permeation speed due to membrane deflection.
  • the moisturizing material 21 is a sheet formed of a hydrophilic material having methanol resistance.
  • hydrophilic material examples include fiber mats, hydrophilic cellulose fibers, and glass fibers.
  • An example of the moisturizing material 21 is “cotton fiber wiper material conveted” manufactured by Asahi Kasei Corporation.
  • the moisturizing material 21 is in direct contact with the force sword electrode 7 through a hole formed in the force sword side collector electrode 2. At this time, the moisturizing material 21 keeps moisture while suppressing evaporation of water from the force sword electrode 7.
  • the moisturizing material 21 may be a sheet formed from a water repellent material.
  • Examples of the water-repellent material include methanol-resistant plastic materials and metal mats. Examples of the methanol-resistant plastic material include PTFE, ETFE, polypropylene, and polyethylene.
  • the moisturizing material 21 keeps the moisture sword electrode 7 sealed in a closed space to suppress evaporation.
  • the moisturizing material 21 may be a sheet in which the hydrophilic material and the water repellent material are combined. At this time, the moisturizing material 21 suppresses the evaporation of water from the force sword electrode 7 and seals the force sword electrode 7 in a closed space to suppress the evaporation and keep the moisture.
  • the polymer electrolyte fuel cell 10 further includes a heat insulating material (not shown).
  • the heat insulating material is formed of a perforated plate and is fixed to the force sword side current collecting electrode 2.
  • the heat insulating material prevents the moisturizing material 21 from being cooled by the outside air.
  • the method for manufacturing the polymer electrolyte fuel cell 10 includes a step of preparing the electrode-electrolyte membrane assembly 3 and a step of manufacturing the polymer electrolyte fuel cell 10.
  • an anode catalyst paste is prepared by stirring a carrier carrying a catalyst and an aqueous solution of a polymer electrolyte.
  • the anode catalyst paste is applied to the porous substrate and dried to produce the anode electrode 6.
  • a force sword catalyst paste is prepared by stirring the carrier carrying the catalyst and the aqueous solution of the polymer electrolyte.
  • the force sword catalyst paste is applied to the porous substrate, and the specified heating temperature is applied.
  • the force sword electrode 7 is manufactured by heating and drying for a predetermined heating time.
  • the solid polymer electrolyte membrane 5 is sandwiched between the anode electrode 6 and the force sword electrode 7 and hot-pressed to prepare the electrode-electrolyte membrane assembly 3. At this time, the solid polymer electrolyte membrane 5 has its anode electrode 6 coated with the anode catalyst paste in contact with the cathode electrode 7 coated with the force sword catalyst paste. It is sandwiched between the anode electrode 6 and the force sword electrode 7.
  • the anode-side collector electrode 1 is arranged so that the anode-side collector electrode 1 is in electrical contact with the anode electrode 6 of the electrode-electrolyte membrane assembly 3.
  • the force sword side collector electrode 2 is the electrode so that 1 is joined to the electrode electrolyte membrane assembly 3 and the force sword side collector electrode 2 is in electrical contact with the force sword electrode 7 of the electrode electrolyte membrane assembly 3 Bonded to the electrolyte membrane assembly 3.
  • the insulating and sealing material 11 is provided with a notch, and a carbon dioxide gas discharge port 14 is formed.
  • Insulating and sealing material 11 has anode-side collector electrode 1 insulated from solid polymer electrolyte membrane 5 and anode electrode 6 exposed to the gap force between solid polymer electrolyte membrane 5 and anode-side collector electrode 1 In order to prevent this, the polymer electrolyte membrane 5 and the anode-side collector electrode 1 are disposed.
  • Insulating and sealing material 12 includes a force sword-side current collecting electrode 2 insulated from the solid polymer electrolyte membrane 5, and a force sword electrode 7 from the gap between the solid polymer electrolyte membrane 5 and the force sword-side current collecting electrode 2. It is disposed between the solid polymer electrolyte membrane 5 and the power sword side collector electrode 2 so as not to be exposed to the outside.
  • the separation membrane 20 is produced by sandwiching a perforated plate 19 between the hydrophilic membrane 17 and the water repellent porous membrane 18.
  • the fuel tank 15 has a fuel holding portion 16 disposed therein.
  • the separation membrane 20 has a fuel tank such that the hydrophilic membrane 17 is in contact with the fuel holding portion 16 and the water-repellent porous membrane 18 is in contact with the anode electrode 6 through the holes of the anode-side collector electrode 1. 15 and the electrode-electrolyte membrane assembly 3.
  • the moisturizing material 21 is directly attached to the force sword electrode 7 through a hole formed in the force sword side collector electrode 2.
  • Anode-side collector electrode 1, force-sword-side collector electrode 2, electrode-electrolyte membrane assembly 3, fuel tank 15, and separation membrane 20 are united using resin screws to form a polymer electrolyte fuel cell 10 is produced.
  • an aqueous methanol solution is stored in the fuel tank 15.
  • the anode side collector electrode 1 and the force sword side collector electrode 2 are electrically connected to the load.
  • the concentration of methanol in the aqueous methanol solution is about 20 v / V % to 70 vZv%.
  • the hydrophilic membrane 17 in contact with the fuel holding portion 16 inside the fuel tank 15 holds the methanol aqueous solution in the membrane, and vaporizes and supplies the fuel as vapor from the membrane surface to the water repellent porous membrane 18.
  • the water repellent porous film 18 supplies the vaporized methanol aqueous solution to the porous substrate of the anode electrode 6.
  • the polymer electrolyte fuel cell 10 generates electricity by supplying an aqueous methanol solution to the porous substrate of the anode electrode 6 and supplying oxygen to the porous substrate of the force sword electrode 7.
  • the electrode reaction expressed by Electrons generated by this electrode reaction are transmitted from the anode electrode 6 to the anode-side collector electrode 1.
  • the electrode reaction expressed by the formula proceeds to generate electric power. Electrons utilized by this electrode reaction are transmitted from the force sword side collector electrode 2 to the force sword electrode 7.
  • the permeation characteristics of the water-repellent porous membrane are substantially the same for methanol and water when fuel is vaporized and supplied. As a result, even if a high-concentration aqueous methanol solution is used, excessive methanol permeation is prevented, and an optimal amount of fuel can be supplied to the anode.
  • the first layer of the hydrophilic membrane oozes out as a slightly liquid with a complete vaporization supply, but the second layer of the membrane is water-repellent, so the liquid fuel directly enters the electrode-electrolyte membrane assembly 3. Leakage can suppress deterioration in characteristics due to crossover.
  • liquid fuel aqueous methanol solution
  • solid fuel examples include a solid fuel obtained by mixing a gelling material and methanol.
  • the solid fuel power fuel component methanol
  • the separation membrane 20 in the above-described embodiment is formed only of the water-repellent porous membrane 18 excluding the hydrophilic membrane 17 and the perforated plate 19. .
  • an anode catalyst paste is prepared by mixing a carrier carrying a catalyst and an aqueous solution of a polymer electrolyte.
  • the catalyst is formed from platinum (Pt) -ruthenium (Ru) alloy fine particles (Ru ratio is 60 at%) having a particle diameter in the range of 3 to 5 nm.
  • the carrier is formed of carbon particles (Ketjen Black EC600JD manufactured by Lion).
  • the polymer electrolyte is formed from DuPont's “Nafion” (registered trademark) (trade name: DE521).
  • the aqueous solution is a 5% by weight aqueous naphthion solution.
  • the anode catalyst paste is applied to a porous substrate and dried to produce an anode electrode 6.
  • the porous substrate is formed of carbon paper (TGP-H-120 made of Torayen earth) and is formed in a square shape of 4 cm ⁇ 4 cm.
  • the anode catalyst paste is applied onto the porous substrate in an amount of 1 mg / cm 2 to 8 mg / cm 2 on the porous substrate.
  • a force sword catalyst paste is prepared by mixing a carrier carrying a catalyst and an aqueous solution of a polymer electrolyte.
  • the catalyst is formed from platinum particles with a particle size in the range of 3-5 nm.
  • the carrier is formed of carbon particles (Ketjen Black EC600JD manufactured by Lion).
  • the polymer electrolyte is formed from “Nafion” (registered trademark) (trade name: DE521) manufactured by DuPont.
  • the aqueous solution is a 5% by weight aqueous naphthion solution.
  • the force sword catalyst paste is applied to the porous base material, and is heated and dried at a predetermined heating temperature for a predetermined heating time, whereby the force sword electrode 7 is manufactured.
  • the porous substrate is formed of carbon paper (TGP-H-120 manufactured by Toray Industries, Inc.) and is formed in a square shape of 4 cm ⁇ 4 cm.
  • the force Sword catalyst paste is applied to the porous lmg / cm 2 ⁇ 8 mg / cm so that the amount of 2 the porous substrate on the substrate.
  • the solid polymer electrolyte membrane 5 is sandwiched between the anode electrode 6 and the force sword electrode 7 and hot-pressed to prepare an electrode-electrolyte membrane assembly 3.
  • the polymer electrolyte membrane 5 is made of DuPont's ⁇ Nafion 117 '' and is formed into a membrane of 8 cm x 8 cm x 180 ⁇ m thickness. It is.
  • the solid polymer electrolyte membrane 5 is in contact with the surface of the anode electrode 6 on which the anode catalyst base is applied, and the surface of the force sword electrode 7 on which the force sword catalyst paste is applied.
  • the anode electrode 6 and the force sword electrode 7 are sandwiched.
  • the anode-side collector electrode 1 is joined to the electrode-electrolyte membrane assembly 3 such that the anode-side collector electrode 1 is in electrical contact with the anode electrode 6 of the electrode-electrolyte membrane assembly 3,
  • the force sword side collector electrode 2 is joined to the electrode-electrolyte membrane assembly 3 so that the force sword side collector electrode 2 is in electrical contact with the force sword electrode 7 of the electrode-electrolyte membrane assembly 3.
  • the anode side current collecting electrode 1 and the force sword side current collecting electrode 2 are each made of stainless steel (SUS316) and formed into a rectangular frame shape having an outer dimension of 6 cm 2 , a thickness of 1 mm, and a width of 11 mm.
  • the insulating and sealing material 11 is formed of a silicone rubber force, and is formed in a rectangular frame shape having an outer dimension of 6 cm 2 , a thickness of 0.2 mm, and a width of 10 mm.
  • the insulating and sealing material 11 is further provided with a cut having a width of 2 mm to form a carbon dioxide gas discharge port 14.
  • Insulating and sealing material 11 has anode-side collector electrode 1 insulated from solid polymer electrolyte membrane 5 and anode electrode 6 exposed to the outside through a gap between solid polymer electrolyte membrane 5 and anode-side collector electrode 1 In order to prevent this, the polymer electrolyte membrane 5 and the anode-side collector electrode 1 are disposed.
  • the insulating and sealing material 12 is formed of a silicone rubber force and is formed in a rectangular frame shape having an outer dimension of 6 cm 2 , a thickness of 0.2 mm, and a width of 10 mm.
  • Insulating and sealing material 12 includes force sword side collector electrode 2 insulated from solid polymer electrolyte membrane 5, and force sword electrode 7 from the gap between solid polymer electrolyte membrane 5 and force sword side collector electrode 2. It is disposed between the solid polymer electrolyte membrane 5 and the power sword side collector electrode 2 so as not to be exposed to the outside.
  • the fuel tank 15 is formed of polypropylene and has an outer dimension of 6 cm 2 , a height of 8 mm, an inner dimension of 44 mm 2 , and a depth of 3 mm.
  • the fuel tank 15 has a fuel holding portion 16 disposed therein.
  • the fuel holding portion 16 is made of a twisting material made of a urethane material.
  • the hydrophilic membrane 17 is made of a material obtained by sulfonating styrene dibutene benzene. 8. 111 80111 Thickness 25 111, Water content 30 / o ion exchange membrane.
  • the hydrophilic film 17 and the water-repellent porous film 18 are made of PTFE, and are formed into a porous film having a size of 8 cm ⁇ 8 cm ⁇ thickness 25 ⁇ m, a pore diameter lum, and a porosity of 85%.
  • the water repellent porous membrane 18 is in contact with the fuel holding portion 16 and is connected to the anode electrode 6 through the hole of the anode side collector electrode 1.
  • the fuel tank 15 and the electrode-electrolyte membrane assembly 3 are sandwiched so as to come into contact with each other.
  • the moisturizing material 21 is directly attached to the force sword electrode 7 through a hole formed in the force sword side collector electrode 2.
  • Moisturizing material 21 is formed from a cellulose fiber sheet (“Cotton Fiber Wiper Material Bencot” manufactured by Asahi Kasei Corporation) and is formed in a 35 mm square.
  • the moisturizing material 21 was fixed to the power sword-side collector electrode 2 by placing a perforated plate having an outer dimension of 6 cm 2 , a thickness of 0.5 mm, a hole diameter of 3 mm and an aperture ratio of 20% as a heat insulating material.
  • the anode side collector electrode 1, the force sword side collector electrode 2, the electrode-electrolyte membrane assembly 3, the fuel tank 15, and the separation membrane 20 are integrated using a resin screw, and the solid polymer type of the comparative example A fuel cell is fabricated.
  • an anode catalyst paste is prepared by mixing a carrier carrying a catalyst and an aqueous solution of a polymer electrolyte.
  • the catalyst is formed from platinum (Pt) -ruthenium (Ru) alloy fine particles (Ru ratio is 60 at%) having a particle diameter in the range of 3 to 5 nm.
  • the carrier is formed from carbon particles (Ketjen Black EC600JD from Lion).
  • the polymer electrolyte is formed from “Nafion” (registered trademark) (trade name: DE521) manufactured by DuPont.
  • the aqueous solution is a 5% by weight aqueous naphthion solution.
  • the anode catalyst paste is applied to the porous substrate and dried to produce the anode electrode 6.
  • the porous substrate is formed of carbon paper (TGP-H-120 made of Torayen earth) and is formed in a square shape of 4 cm ⁇ 4 cm.
  • the anode catalyst paste is applied onto the porous substrate in an amount of 1 mgZcm 2 to 8 mgZcm 2 on the porous substrate.
  • a sword catalyst paste is prepared by mixing a carrier carrying a catalyst and an aqueous solution of a polymer electrolyte.
  • the catalyst is formed from platinum particles with a particle size in the range of 3-5 nm.
  • the carrier is formed of carbon particles (Ketchin Black EC600JD manufactured by Lion Corporation).
  • the polymer electrolyte is formed from “Nafion” (registered trademark) (trade name: DE521) manufactured by DuPont.
  • the aqueous solution is a 5% by weight aqueous naphthion solution.
  • the porous substrate is formed of carbon paper (TGP-H-120 manufactured by Toray Industries, Inc.) and is formed in a square shape of 4 cm ⁇ 4 cm.
  • the force Sword catalyst paste is applied to the porous lmg / cm 2 ⁇ 8 mg / cm so that the amount of 2 the porous substrate on the substrate.
  • the solid polymer electrolyte membrane 5 is sandwiched between the anode electrode 6 and the force sword electrode 7 and hot-pressed to prepare the electrode-electrolyte membrane assembly 3.
  • the solid polymer electrolyte membrane 5 is made of “Nafion 117” manufactured by DuPont, and is formed into a membrane of 8 cm ⁇ 8 cm ⁇ 180 ⁇ m thick. At this time, the solid polymer electrolyte membrane 5 is in contact with the surface of the anode electrode 6 on which the anode catalyst base is applied, and the surface of the force sword electrode 7 on which the force sword catalyst paste is applied. The anode electrode 6 and the force sword electrode 7 are sandwiched.
  • the anode side collector electrode 1 is joined to the electrode electrolyte membrane assembly 3 so that the anode side collector electrode 1 is in electrical contact with the anode electrode 6 of the electrode electrolyte membrane assembly 3, and the force sword
  • the force sword-side collector electrode 2 is joined to the electrode electrolyte membrane assembly 3 such that the side collector electrode 2 is in electrical contact with the force sword electrode 7 of the electrode electrolyte membrane assembly 3.
  • the anode side current collecting electrode 1 and the force sword side current collecting electrode 2 are each made of stainless steel (SUS316) and formed into a rectangular frame shape having an outer dimension of 6 cm 2 , a thickness of 1 mm, and a width of 11 mm.
  • the insulating and sealing material 11 is formed of a silicone rubber force, and is formed in a rectangular frame shape having an outer dimension of 6 cm 2 , a thickness of 0.2 mm, and a width of 10 mm.
  • the insulating and sealing material 11 is further provided with a cut having a width of 2 mm to form a carbon dioxide gas discharge port 14.
  • Insulating and sealing material 11 has anode-side collector electrode 1 insulated from solid polymer electrolyte membrane 5 and anode electrode 6 exposed to the outside through a gap between solid polymer electrolyte membrane 5 and anode-side collector electrode 1 In order to prevent this, the polymer electrolyte membrane 5 and the anode-side collector electrode 1 are disposed.
  • the insulating and sheathing material 12 is formed of silicon rubber and is formed in a rectangular frame shape having an outer dimension of 6 cm 2 , a thickness of 0.2 mm, and a width of 10 mm.
  • Insulating and sealing material 12 includes force sword side collector electrode 2 insulated from solid polymer electrolyte membrane 5, and force sword electrode 7 from the gap between solid polymer electrolyte membrane 5 and force sword side collector electrode 2. It is disposed between the solid polymer electrolyte membrane 5 and the power sword side collector electrode 2 so as not to be exposed to the outside.
  • the separation membrane 20 is manufactured by sandwiching a perforated plate 19 between the hydrophilic membrane 17 and the water repellent porous membrane 18.
  • the hydrophilic membrane 17 is made of a material obtained by sulfonating styrene dibutene benzene. 8. 111 80111 Thickness 25 111, Water content 30 / o ion exchange membrane.
  • the water repellent porous film 18 is made of PTFE, and is formed into a porous film having a thickness of 25 xm, a pore diameter lum, and a porosity of 85%.
  • the perforated plate 19 is made of SUS316 stainless steel, is formed in a plate shape having an outer dimension of 6 cm 2 and a thickness of 1 mm, and has a hole diameter of 4 mm and an aperture ratio of 70%.
  • the fuel tank 15 is formed of polypropylene and has an outer dimension of 6 cm 2 , a height of 8 mm, an inner dimension of 44 mm 2 , and a depth of 3 mm.
  • the fuel tank 15 has a fuel holding portion 16 disposed therein.
  • the fuel holding portion 16 is made of a twisting material made of a urethane material.
  • the separation membrane 20 has a fuel tank such that the hydrophilic membrane 17 is in contact with the fuel holding portion 16 and the water-repellent porous membrane 18 is in contact with the anode electrode 6 through the holes of the anode-side collector electrode 1. 15 and the electrode electrolyte membrane assembly 3.
  • the moisturizing material 21 is directly attached to the force sword electrode 7 through a hole formed in the force sword side collector electrode 2.
  • the moisturizing material 21 is formed from a cellulose fiber sheet (“Cotton Fiber Wiper Material Bencot” manufactured by Asahi Kasei Corporation) and is formed in a 35 mm square.
  • the moisturizing material 21 was fixed to the power sword-side collector electrode 2 by placing a perforated plate having an outer dimension of 6 cm 2 , a thickness of 0.5 mm, a hole diameter of 3 mm and an aperture ratio of 20% as a heat insulating material.
  • the anode side collector electrode 1, the force sword side collector electrode 2, the electrode-electrolyte membrane assembly 3, the fuel tank 15, and the separation membrane 20 are integrated using a resin screw to form the solid polymer type of the example
  • the fuel cell 10 is manufactured.
  • FIG. 3 shows the power generation characteristics of the polymer electrolyte fuel cell of the comparative example and the power generation characteristics of the polymer electrolyte fuel cell of the experimental example.
  • This output time characteristic is that when 50vol% _methanol aqueous solution is supplied to the fuel tank 15 of the electrode / electrolyte membrane assembly, when 1A is discharged at room temperature (25 ° C), the time of the starting force of the discharge The electromotive force of the electrode-electrolyte membrane assembly with respect to is shown.
  • the power generation characteristic 31 of the polymer electrolyte fuel cell of the comparative example shows that the electromotive force has a maximum value in the initial stage, and the electromotive force gradually decreases as time passes after showing the maximum value. .
  • the electromotive force has a maximum value at the initial stage, and the electromotive force increases with time after showing the maximum value. It shows a gradual decrease.
  • the graph in FIG. 3 shows that the voltage of the polymer electrolyte fuel cell of the experimental example is higher than the voltage of the polymer electrolyte fuel cell of the comparative example, and the polymer electrolyte fuel cell according to the present invention stabilizes the high voltage. Indicates that it can be output.
  • the comparative example is a fuel cell configured by removing the perforated plate and the hydrophilic membrane from the fuel cell of the experimental example.
  • This experimental result shows that the force sword electrode during discharge of the polymer electrolyte fuel cell of the comparative example is 60 ° C, and the force sword electrode during discharge of the polymer electrolyte fuel cell of the example is Indicates 35 ° C.
  • This experimental result shows that the temperature increase of the force sword electrode in the experimental example is suppressed to the extent expected from the calorific value of the polymer electrolyte fuel cell.
  • This experimental result further shows that the activity of the catalyst of the force sword electrode during discharge of the polymer electrolyte fuel cell of the experimental example is lower than that of the example, and the methanol permeation amount of the polymer electrolyte fuel cell of the comparative example This shows that methanol crosses over to the side of the force sword electrode.
  • This experimental result shows that the polymer electrolyte fuel cell according to the present invention supplies fuel more appropriately to the electrode / electrolyte membrane assembly.
  • This experimental result further shows that the fuel consumption of the polymer electrolyte fuel cell of the comparative example is 2 g / h, and the fuel consumption of the polymer electrolyte fuel cell of the example is 0.5 g / h. It shows that there is.
  • This experimental result shows that the fuel utilization efficiency of the polymer electrolyte fuel cell of the experimental example is better than the fuel utilization efficiency of the polymer electrolyte fuel cell of the comparative example, and is necessary for such a load current value. Since the fuel is 0.33 g / h, it is shown that the fuel utilization efficiency of the solid polymer fuel cell according to the present invention is good.
  • the experimental results show that the polymer electrolyte fuel cell of the experimental example uses a very high concentration and 50% methanol solution, and despite its high concentration methanol aqueous solution, high output and low fuel consumption are realized. It shows that it is possible.
  • the polymer electrolyte fuel cell according to the present invention can supply the optimum fuel.
  • the first hydrophilic membrane in contact with the liquid fuel layer holds the liquid fuel in the membrane, and vaporizes and supplies the fuel as vapor from the membrane surface. Have a role to play.
  • fuel is supplied as vapor to the second water-repellent porous membrane adjacent to the hydrophilic membrane.
  • conventional liquid fuel is supplied directly to the water-repellent porous membrane Since methanol permeation is large and water permeation is small, methanol permeation becomes dominant when a high-concentration methanol aqueous solution is used, resulting in water shortage at the anode and an increase in methanol crossover to the power sword. The power generation characteristics were not sufficient.
  • the permeation characteristics of the water-repellent porous membrane are almost the same for methanol and water.
  • the first layer of the hydrophilic membrane oozes out as a slightly liquid with a completely vaporized supply, but the second layer of the membrane is water-repellent so that the liquid fuel does not leak directly into the MEA. It is possible to suppress deterioration of characteristics due to the above.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

L’invention concerne une pile à combustible (10) à polymère solide comprenant un ensemble membrane-électrode (3) destiné à générer de l’électricité par réaction chimique entre un combustible et un agent oxydant, une membrane hydrophile (17) constituée d’un matériau hydrophile et une membrane poreuse (18) hydrofuge constituée d’un matériau hydrofuge. Ladite membrane poreuse hydrofuge (18) est disposée entre l’ensemble membrane-électrode (3) et la membrane hydrophile (17). Le combustible est fourni à l’ensemble membrane-électrode (3) à travers la membrane hydrophile (17) et la membrane poreuse hydrofuge (18). Une perméation excessive du combustible peut être évitée dans ladite pile à combustible (10) à polymère solide même lorsqu’une solution aqueuse de combustible de concentration élevée est utilisée, ce qui permet d’éviter une pénurie d’eau au niveau d’une anode (6) ou une augmentation du passage de combustible vers une cathode (7). Il est ainsi possible d’éviter la dégradation des caractéristiques de la pile à combustible (10) à polymère solide et d’obtenir des caractéristiques de génération d’électricité satisfaisantes.
PCT/JP2006/325540 2006-01-16 2006-12-21 Pile a combustible a polymere solide WO2007080763A1 (fr)

Priority Applications (3)

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US12/160,985 US7923164B2 (en) 2006-01-16 2006-12-21 Solid polymer fuel cell
CN2006800512200A CN101361216B (zh) 2006-01-16 2006-12-21 固体高分子型燃料电池
JP2007553863A JP5182559B2 (ja) 2006-01-16 2006-12-21 固体高分子型燃料電池

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JP2006007657 2006-01-16

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JP2009081111A (ja) * 2007-09-27 2009-04-16 Sony Corp 燃料電池
JP2009146616A (ja) * 2007-12-11 2009-07-02 Toshiba Corp 燃料電池
WO2010007818A1 (fr) * 2008-07-16 2010-01-21 日本電気株式会社 Pile à combustible à polymère solide
JP2013054836A (ja) * 2011-09-01 2013-03-21 Fujikura Ltd ダイレクトメタノール型燃料電池の燃料供給装置
US8524418B2 (en) 2007-02-22 2013-09-03 Nec Corporation Polymer electrolyte fuel cell
JP2013200972A (ja) * 2012-03-23 2013-10-03 Fujikura Ltd ダイレクトメタノール型燃料電池
WO2015034088A1 (fr) 2013-09-06 2015-03-12 株式会社 エム光・エネルギー開発研究所 Dispositif de réaction électrochimique comprenant un film poreux anti-liquide
US10981138B2 (en) 2016-04-13 2021-04-20 M Hikari & Energy Laboratory Co., Ltd. Electrochemical reactor using ion on/off surface switch

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JP2002280016A (ja) * 2001-03-16 2002-09-27 Samsung Electronics Co Ltd ダイレクトメタノール燃料電池用単電極型セルパック
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US8524418B2 (en) 2007-02-22 2013-09-03 Nec Corporation Polymer electrolyte fuel cell
JP2009081111A (ja) * 2007-09-27 2009-04-16 Sony Corp 燃料電池
JP2009146616A (ja) * 2007-12-11 2009-07-02 Toshiba Corp 燃料電池
WO2010007818A1 (fr) * 2008-07-16 2010-01-21 日本電気株式会社 Pile à combustible à polymère solide
JP2013054836A (ja) * 2011-09-01 2013-03-21 Fujikura Ltd ダイレクトメタノール型燃料電池の燃料供給装置
JP2013200972A (ja) * 2012-03-23 2013-10-03 Fujikura Ltd ダイレクトメタノール型燃料電池
WO2015034088A1 (fr) 2013-09-06 2015-03-12 株式会社 エム光・エネルギー開発研究所 Dispositif de réaction électrochimique comprenant un film poreux anti-liquide
KR20160052560A (ko) 2013-09-06 2016-05-12 엠 히카리 앤 에너지 레보레토리 컴퍼니 리미티드 발액성 다공질막을 구비한 전기화학반응 장치
RU2660125C2 (ru) * 2013-09-06 2018-07-05 М Хикари Энд Энерджи Лэборетери Ко., Лтд. Электрохимический реактор, содержащий отталкивающую жидкость пористую мембрану
US10407780B2 (en) 2013-09-06 2019-09-10 M Hikari & Energy Laboratory Co., Ltd. Electrochemical reactor comprising liquid-repellent porous membrane
US11459662B2 (en) 2013-09-06 2022-10-04 M Hikari & Energy Laboratory Co., Ltd. Electrochemical reactor comprising liquid-repellant porous membrane
US10981138B2 (en) 2016-04-13 2021-04-20 M Hikari & Energy Laboratory Co., Ltd. Electrochemical reactor using ion on/off surface switch

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US7923164B2 (en) 2011-04-12
CN101361216A (zh) 2009-02-04
US20100203418A1 (en) 2010-08-12
JPWO2007080763A1 (ja) 2009-06-11
CN101361216B (zh) 2010-12-15

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